EP0034704B1 - Schlagzähe Polyamidmischungen und Verfahren zu deren Herstellung - Google Patents

Schlagzähe Polyamidmischungen und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0034704B1
EP0034704B1 EP81100431A EP81100431A EP0034704B1 EP 0034704 B1 EP0034704 B1 EP 0034704B1 EP 81100431 A EP81100431 A EP 81100431A EP 81100431 A EP81100431 A EP 81100431A EP 0034704 B1 EP0034704 B1 EP 0034704B1
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EP
European Patent Office
Prior art keywords
nylon
weight
carboxyl
acid
blend
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81100431A
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English (en)
French (fr)
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EP0034704A1 (de
Inventor
Miguel Jacinto Roura
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EIDP Inc
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EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene

Definitions

  • This invention relates to polyamide molding materials, and more particularly to polyamide blends which are toughened by polymeric tougheners.
  • Blends on the basis of polyamides and olefinic copolymers with carboxyl functionality are known from Canadian Patent 740,501, thermoplastic compositions having specific physical characteristics being concerned. Nylon 66, nylon 610, nylon 6, copolymers of nylon 66 and nylon 610 as well as of nylon 66 and nylon 6 and blends of those polyamides come under consideration.
  • the olefinic copolymers with carboxyl functionality are illustrated on pages 5-6 of the patent. The patent is primarily concerned with making compositions available which are suited for producing bottles, and, therefore, are to exhibit an improved barrier effect over against pure polyamides but are, as to the rest, not to exhibit any deteriorated physical characteristics.
  • Blends on the basis of polyamides and olefinic copolymers with carboxyl functionality are also known from French Patent 2,372,866. Molded articles of those blends are said to be resistant to shock.
  • This invention provides a blend on the basis of polyamides and olefinic copolymers having carboxyl functionality.
  • the blend has good impact strength and ductility at low temperatures, e.g. 0°C, and comprises:
  • elastomeric is meant that the copolymer after molding will assume substantially its original shape after distortion causing pressure is removed.
  • olefinic is meant terminally unsaturated monomers including dienes.
  • copolymer is meant a polymer composed of two or more different monomeric units.
  • the blend must contain no less than 20% and no more than 80% 6 nylon.
  • compositions containing 66 nylon alone or 6 nylon alone have lower toughening at low temperatures for a given toughener.
  • the behavior of 66 and 6 nylon blends is unique in that compositions based on other nylon blends such as 6/612 or 66/612 nylon have low temperature toughness inferior to compositions containing one of the two nylon components.
  • 66 Nylon and 6 nylon are commonly known and available.
  • 66 Nylon is polyhexamethylene- adipamide, while 6 nylon is polycaprolactam. Both are high molecular weight polymers, i.e., of film- forming molecular weight.
  • Toughening component b) (ii) is a polymer of ethylene, at least one C 3 C 6 a-olefin and at least one nonconjugated diene, the polymer having carboxyl or carboxylate functionality.
  • Propylene is normally selected as the C 3 -C 6 a-olefin in preparing such polymers.
  • Other C 3 -C 6 a-olefins, namely 1-butene, 1-pentene, and 1-hexene can be selected in place of or in addition to propylene in preparing the elastomeric polymers.
  • the nonconjugated diene is monoreactive.
  • Monoreactive nonconjugated dienes have one double bond which readily enters the polymerization reaction with ethylene and propylene, and a second double bond which does not, to any appreciable extent, enter the polymerization reaction.
  • Monoreactive nonconjugated dienes include linear aliphatic dienes of at least six carbon atoms which have one terminal double bond and one internal double bond, and cyclic dienes wherein one or both of the carbon-to-carbon double bonds are part of a carbocyclic ring.
  • the nonconjugated diene can also be a direactive one.
  • direactive is meant that both double bonds are capable of polymerizing during preparation of the polymer.
  • direactive dienes include 2,5-norbornadiene and 1,7-octadiene.
  • the carboxyl or carboxylate functionality is ordinarily supplied by employing as a comonomer in the copolymer an ethylenically unsaturated comonomer containing carboxyl or carboxylate groups.
  • the comonomers are a lower alkyl acrylate or methacrylate, such as methyl acrylate, ethyl acrylate, or isobutyl acrylate, or other olefins or mixtures thereof.
  • the comonomers can also be methacrylic or acrylic acid, fumaric acid, maleic anhydride or glycidyl methacrylate.
  • the carboxyl or carboxylate functionality can also be supplied by reacting the ethylene/C 3 -C 6 ⁇ -olefin/unconjugated diene with an unsaturated compound taken from the class consisting of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having from 4 to 8 carbon atoms, or derivatives thereof.
  • unsaturated compound taken from the class consisting of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having from 4 to 8 carbon atoms, or derivatives thereof.
  • Such derivatives include monoesters of alcohols of 1 to 29 carbon atoms, anhydrides of the dicarboxylic acids, or the metal salts of the acids, or the monoester of the dicarboxylic acid having from 0 to 100 percent of the carboxylic acid groups ionized by neutralization with metal basic salt.
  • acids and derivatives are maleic acid, maleic anhydride, maleic acid monoethyl ester, metal salts of maleic acid monoethyl ester, fumaric acid, fumaric acid monoethyl ester, itaconic acid, vinyl benzoic acid, vinyl phthalic acid, metal salts of fumaric acid monoethyl ester, monoesters of maleic or fumaric acid or itaconic acids where the alcohol is methyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, 2-ethyl hexyl, decyl, stearyl, methoxy ethyl, ethoxy ethyl and hydroxy ethyl.
  • the adducts can be prepared by any grafting process which intimately mixes the unsaturated acid or derivative with the polymer without appreciable generation of free radicals, and which concurrently or subsequently heats the mixture to a temperature whereat thermal addition occurs. Selected temperatures will generally be at least 225°C to obtain adduct formation at acceptable rates and less than about 450°C to avoid any excessive polymer breakdown. Preferred temperature ranges will vary with the particular polymer and can readily be determined by one skilled in the art.
  • Mixing of the acid or derivative and polymer can be by blending in an internal mixer or extruder, or by blending finely divided dry compound with polymer on a well-ventilated rubber mill with concurrent or subsequent heating, such as in a hot press or mold.
  • the acid or derivative can be substituted with groups, such as bromine or chlorine, which do not unduly interfere with the graft reaction.
  • adducts containing about 0.5 to 9 percent, and preferably about 1 to 4 percent, by weight of the acid or derivative.
  • the diene is 1,4-hexadiene
  • the C 3- C 6 a-olefin is propylene
  • the unsaturated compound having carboxyl or carboxylate functionality is fumaric acid.
  • Toughening component b) (ii) is derived from an a-olefin and an a,j3-unsaturated carboxylic acid, and optionally other copolymerizable comonomers.
  • the acid moiety is at least partially ionized by neutralizing with metal basic salts.
  • the a-olefin is ethylene and the acid is acrylic or methacrylic acid.
  • the other copolymerizable comonomer can be an acrylate or methacrylate.
  • the metal ion can be monovalent, divalent or trivalent, as for example Na, Zn, Al, K.
  • a representative toughening component b) (ii) is for example:
  • the blends of the present invention are prepared by admixing the ingredients in the indicated proportions and melt blending them for intimate admixture.
  • the 6 nylon, 66 nylon and toughening polymer or polymers are first mixed by tumbling in a drum.
  • the melt blending typically can be conducted at a temperature above the melting point of the components and below the decomposition temperature. A temperature range of about from 260°C to 330°C is preferred.
  • the blends are particularly useful in applications in which impact strength is important at low temperatures, such as in automobile bumpers, sports equipment or safety equipment.
  • the blends of this invention may also contain one or more conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation; lubricants and mold release agents, colorants including dyes and pigments, flame-retardants, fibrous and particulate fillers and reinforcements and plasticizers. These additives are commonly added during the mixing step.
  • oxidative and thermal stabilizers which may be present in blends of the present invention include Group I metal halides, e.g., sodium, potassium, lithium with cuprous halides, e.g., chloride, bromide, iodide; hindered phenols, hydroquinones, and varieties of substituted members of those groups and combinations thereof.
  • Group I metal halides e.g., sodium, potassium, lithium
  • cuprous halides e.g., chloride, bromide, iodide
  • hindered phenols e.g., hydroquinones, and varieties of substituted members of those groups and combinations thereof.
  • Representative ultraviolet light stabilizers include various substituted resorcinols, salicylates, benzotriazoles and benzophenones.
  • Representative lubricants and mold release agents include stearic acid, stearyl alcohol, and stearamides.
  • Representative organic dyes include nigrosine, while representative pigments, include titanium dioxide, cadmium sulfide, cadmium selenide, phthalocyanines, ultramarine blue and carbon black.
  • Representative fillers include carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, and feldspar.
  • Representative flame-retardants include organic halogenated compounds such as decabromodiphenyl ether.
  • the ingredients were blended by tumbling in a drum.
  • the mixture was then pelletized by melt blending in a Werner & Pfleiderer twin screw extruder at a barrel temperature of between 310-320°C and a die temperature of 290°C. Extrusion was carried out with a port open to the air or under vacuum when removing monomeric caprolactam was desired. The screw speed was 200 rpm.
  • the resulting strand was quenched in water, but into pellets, and sparged with nitrogen until cold to remove moisture.
  • the 66 nylon used had a relative viscosity of about 52; while the 6 nylon used had a relative viscosity of between 75-90, tested in an 8.4% polymer solution in 90% formic acid.
  • EPDM used in the tables and examples stands for a copolymer composed of 72 percent ethylene, 24 percent propylene, and 4 percent 1,4-hexadiene. It is employed as an extender for the toughening polymer.
  • EPDM-FA stands for a toughening copolymer composed of 68% ethylene, 26% propylene, 6% 1,4-hexadiene and 0.06% 2,5-norbornadiene which is treated with fumaric acid to result in an adduct having 1.5-2.0% functionality, acid and anhydride, as measured by Infrared (CPE 671 Spectrophotometer), and 1.2-4.8 g/10 min melt flow at 280°C through a 0.0325 cm diameter orifice.
  • CPE 671 Spectrophotometer Infrared

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

1. Gemisch von Polyamiden und olefinischen Copolymeren mit Carboxylfunktionalität, enthaltend
(a) 60-97 Gew.-% Polyamid, bei dem es sich um ein Gemisch von 20-80 Gew.-% Nylon-66 und ergänzend 80-20 Gew.-% Nylon-6 handelt, und ergänzend
(b) 3-40 Gew.-% eines polymeren zähmachenden Mittels ausgewählt entweder aus
(i) einem elastomeren olefinischen Copolymeren mit Carboxyl- oder Carboxylatfunktionalität, bei dem es sich um ein Addukt eines Polymeren von Ethylen, mindestens einem C3-C6-α-Olefin und mindestens einem nicht-konjugierten Dien mit einer ethylenisch ungesättigten Verbindung mit Carboxyl- oder Carboxylatfunktionalität handelt, oder
(ii) einem ionischen Copolymeren von mindestens einem a-Olefin und mindestens einer a,f3-unge- sätigten Carbonsäure, das ein drittes copolymerisierbares Monomeres enthalten kann, worin der Säurerest zumindest teilweise durch Neutralisieren mit basischen Metallsalzen ionisiert ist.
2. Gemisch nach Anspruch 1, worin die Komponente (b) (ii) ein Copolymeres von Ethylen/Isobutylacrylat/Methacrylsäure ist, das zu 70% mit Zink neutralisiert ist.
3. Gemisch nach Anspruch 1 oder 2, worin die Komponente (b) in einer Menge von 10-30 Gew.-% vorhanden ist.
4. Gemisch nach den Ansprüchen 1 bis 3, worin in (b) (i) das Dien 1,4-Hexadien, das C3-C6-α-Olefin Propylen und die ungesättigte Verbindung mit Carboxyl- oder Carboxylatfunktionalität Fumarsäure ist.
5. Verfahren zur Herstellung des Harzes nach den Ansprüchen 1 bis 4, bei dem die Komponenten physikalisch gemischt und anschließend schmelzcompoundiert werden.
EP81100431A 1980-01-22 1981-01-22 Schlagzähe Polyamidmischungen und Verfahren zu deren Herstellung Expired EP0034704B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11424080A 1980-01-22 1980-01-22
US114240 1980-01-22
US198356 1980-10-20
US06/198,356 US4346194A (en) 1980-01-22 1980-10-20 Toughened polyamide blends

Publications (2)

Publication Number Publication Date
EP0034704A1 EP0034704A1 (de) 1981-09-02
EP0034704B1 true EP0034704B1 (de) 1984-04-11

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EP81100431A Expired EP0034704B1 (de) 1980-01-22 1981-01-22 Schlagzähe Polyamidmischungen und Verfahren zu deren Herstellung

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US (1) US4346194A (de)
EP (1) EP0034704B1 (de)
CA (1) CA1144682A (de)
DE (1) DE3163017D1 (de)

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EP0034704A1 (de) 1981-09-02
US4346194A (en) 1982-08-24
DE3163017D1 (en) 1984-05-17

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